Azo dye having a 3-cyano- or 3-carbamoyl-2,6-diaminopyridine coupling component

ABSTRACT

A disazo dye derived from a pyridine coupling component and having the general formula ##STR1## where X is fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, cyano, nitro, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, a carboxylic acid ester group of 2 to 11 carbon atoms, carbamoyl or C 1  -C 8  -N-monosubstituted or -N,N-disubstituted carbamoyl or sulfamoyl, 
     Y 1  is hydrogen, chlorine, bromine, nitro, methyl or cyano, 
     Y 2  is hydrogen, chlorine, bromine or methoxy, 
     Z is cyano or carbamoyl, 
     R is hydrogen or C 1  -C 3  -alkyl, 
     R 1  is hydrogen, methyl, ethyl or C 1  -C 4  -alkoxy, 
     R 2  is methyl, ethyl or C 1  -C 4  -alkoxy, 
     the radicals B 1  independently or one another are hydrogen or an aliphatic, cycloaliphatic, araliphatic or aromatic radical and 
     B 2  is hydrogen or unsubstituted or substituted alkyl, or 
     B 1  and B 2  together with the nitrogen are a saturated 5-membered to 7-membered ring. 
     The present dyes exhibit excellent fastness properties when utilized in the dyeing and printing of polyester and cotton fabrics as well as polyester/cotton union fabrics.

The present invention relates to disazo dyes. According to the invention there are provided compounds of the general formula I ##STR2## where X is fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, cyano, nitro, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, a carboxylic acid ester group of 2 to 11 carbon atoms, carbamoyl or C₁ -C₈ -N-monosubstituted or -N,N-disubstituted carbamoyl or sulfamoyl,

Y¹ is hydrogen, chlorine, bromine, nitro, methyl or cyano,

Y² is hydrogen, chlorine, bromine or methoxy,

Z is cyano or carbamoyl,

R is hydrogen or C₁ -C₃ -alkyl,

R¹ is hydrogen, methyl, ethyl or C₁ -C₄ -alkoxy,

R² is methyl, ethyl or C₁ -C₄ -alkoxy,

the radicals B¹ independently of one another are hydrogen or an aliphatic, cycloaliphatic, araliphatic or aromatic radical and

B² is hydrogen or unsubstituted or substituted alkyl, or

B¹ and B² together with the nitrogen are a saturated 5-membered to 7-membered ring.

Specific examples of radicals X, in addition to those already mentioned, are: COOCH₃, COOC₂ H₅, COOC₃ H₇, COOC₄ H₉, COOC₆ H₁₃, COOC₈ H₁₇, ##STR3## COOC₁₀ H₂₁, COOC₂ H₄ OCH₃, COOC₂ H₄ OC₂ H₅, COOC₂ H₄ OC₄ H₉, COOC₂ H₄ OC₆ H₅, COOC₃ H₆ OH, COOC₆ H₁₂ OH, COOC₃ H₆ -O-C₄ H₈ -OH, CONHCH₃, CONHC₂ H₅, CONHC₃ H₇, CONHC₄ H₉, CONHC₆ H₁₃, ##STR4## CONHC₂ H₄ OH, CONHC₂ H₄ OCH₃, CON(CH₃)₂, CON(C₂ H₅)₂, CON(C₃ H₇)₂, CON(C₄ H₉)₂, ##STR5## and CON(C₂ H₄ -OCH₃)₂.

Examples of substituents B¹, other than hydrogen, are alkyl of 1 to 8 carbon atoms, allyl, C₂ -C₈ -alkyl substituted by hydroxyl, cyano, alkoxy of 1 to 8 carbon atoms, phenoxy, phenoxyethoxy or benzyloxy, cyclohexyl, norbornyl, benzyl, phenylethyl, phenylhydroxyethyl, phenylpropyl, phenylbutyl, phenyl which is unsubstituted or substituted by chlorine, methyl, trifluoromethyl, pyrrolidonyl, methoxy or ethoxy, C₅ -C₁₂ -polyalkoxyalkyl, C₄ -C₉ -hydroxypolyalkoxyalkyl, C₁ -C₈ -alkanoyloxy-C₂ -C₆ -alkyl, C₇ -C₁₁ -aroyloxy-C₂ -C₆ -alkyl, C₁ -C₈ -alkylaminocarbonyloxy-C₂ -C₆ -alkyl, C₆ -C₁₀ -arylaminocarbonyloxy-C₂ -C₆ -alkyl, C₁ -C₈ -alkoxycarbonyl-C₂ -C₇ -alkyl, C₁ -C₁₈ -alkanoyl, C₈ -C₁₀ -aralkanoyl, C₇ -C₁₁ -aroyl, C₁ -C₄ -alkylsulfonyl and C₆ -C₁₀ -arylsulfonyl.

Specific examples of radicals B¹, in addition to those already mentioned, are:

1. unsubstituted and substituted alkyl:

CH₃, C₂ H₅, n- and i-C₃ H₇, n- and i-C₄ H₉, C₆ H₁₃, ##STR6## CH₂ CH₂ OH, (CH₂)₃ OH, ##STR7## (CH₂)₄ OH, (CH₂)₆ OH, ##STR8## (CH₂)₂ O(CH₂)₂ OH, (CH₂)₃ O(CH₂)₄ OH, (CH₂)₃ O(CH₂)₂ OH, (CH₂)₂ CN, (CH₂)₅ CN, (CH₂)₆ CN, (CH₂)₇ CN, (CH₂)₂ O(CH₂)₂ CN, (CH₂)₃ O(CH₂)₂ CN, (CH₂)₂ O(CH₂)₂ O(CH₂)₂ CN, (CH₂)₃ O(CH₂)₂ OCH₃, (CH₂)₃ O(CH₂)₂ OCH₂ H₅, (CH₂)₃ O(CH₂)₆ OH, (CH₂)₃ O(CH₂)₂ OCH(CH₃)₂, (CH₂)₃ O(CH₂)₂ OC₄ H₉, (CH₂)₃ O(CH₂)₂ OCH₂ C₆ H₅, (CH₂)₃ O(CH₂)₂ O(CH₂)₂ C₆ H₅, ##STR9## (CH₂)₃ O(CH₂)₂ OC₆ H₅, ##STR10## and the corresponding radicals in which the groups --O(CH₂)₂ --, ##STR11## occur two or three times, CH₂ CH₂ OCH₃, CH₂ CH₂ OC₂ H₅, CH₂ CH₂ OC₃ H₇, CH₂ CH₂ OC₄ H₉, CH₂ CH₂ OC₆ H₅, (CH₂)₃ OCH₃, (CH₂)₃ OC₂ H₅, (CH₂)₃ OC₃ H₇, (CH₂)₃ OC₄ H₉, ##STR12## (CH₂)₃ OC₆ H₁₃, (CH₂)₃ OC₈ H₁₇, (CH₂)₃ OCH₂ C₆ H₅, (CH₂)₃ OC₂ H₄ C₆ H₅, (CH₂)₃ OC₆ H₅,

2. unsubstituted and substituted cycloalkyl and polycycloalkyl: ##STR13##

3. Aralkyl:

CH₂ C₆ H₅, C₂ H₄ C₆ H₅, ##STR14## and corresponding radicals with C₆ H₄ CH₃ in place of C₆ H₅.

4. Unsubstituted and substituted phenyl:

C₆ H₅, C₆ H₄ CH₃, C₆ H₃ (CH₃)₂, C₆ H₄ OCH₃, C₆ H₄ OC₂ H₅, C₆ H₄ OCH₂ CH₂ OH and C₆ H₄ Cl;

5. the following radicals:

CH₂ CH═CH₂, CH₂ COOCH₃, (CH₂)₅ COOCH₃, (CH₂)₅ COOC₂ H₅, (CH₂)₅ COOC₄ H₉, ##STR15## where n is 2, 3, 4 or 6.

6. Acyloxy:

(CH₂)₂ OCHO, (CH₂)₂ OCOCH₃, (C₂ H₄ O)₂ CHO, (C₂ H₄ O)₂ COCH₃, (CH₂)₂ OCOC₃ H₇, ##STR16## (CH₂)₂ OCOC₆ H₅, (CH₂)₂ OCOC₆ H₄ CH₃, (CH₂)₂ OCOC₆ H₄ Cl, (CH₂)₂ OCOC₁₀ H₇, (CH₂)₂ OCONHCH₃, (CH₂)₂ OCONHC₄ H₉, ##STR17## (CH₂)₂ OCONHC₆ H₅, (CH₂)₂ OCONHC₆ H₄ Cl, (CH₂)₂ OCONHC₆ H₃ Cl₂, and the corresponding radicals which respectively contain (CH₂)₃, (CH₂)₄ or (CH₂)₆ in place of (CH₂)₂.

7. Acyl:

CHO, CH₃ CO, C₂ H₅ CO, C₃ H₇ CO, ##STR18## C₂ H₅ CO, CH₃ C₆ H₄ CO, C₆ H₅ CH₂ CO, C₆ H₅ OCH₂ CO, CH₃ SO₂, C₂ H₅ SO₂, C₆ H₅ SO₂ and CH₃ C₆ H₄ SO₂.

Examples of preferred substituents are hydrogen, C₂ H₅, n- and i-C₃ H₇, n- and i-C₄ H₉, C₆ H₁₃, (CH₂)₆ OH, ##STR19## (CH₂)₃ O(CH₂)₂ OH, (CH₂)₃ O(CH₂)₄ OH, (CH₂)₃ O(CH₂)₆ OH, ##STR20## (n=2, 3, 6), CH₂ CH₂ OCH₃, CH₂ CH₂ OC₂ H₅, CH₂ CH₂ OC₄ H₉, (CH₂)₃ OCH₃, (CH₂)₃ OC₂ H₅, (CH₂)₃ OC₃ H₇, (CH₂)₃ OC₄ H₉, ##STR21## (CH₂)₃ OC₂ H₄ OCH₃, (CH₂)₃ OC₂ H₄ OC₄ H₉, (CH₂)₃ OC₂ H₄ OC₆ H₅, ##STR22## CH₂ C₆ H₅, C₂ H₄ C₆ H₅, ##STR23## C₆ H₅, C₆ H₄ CH₃, C₆ H₄ OCH₃ and C₆ H₄ OC₂ H₄ OH and the corresponding radicals with C₆ H₄ CH₃ in place of C₆ H₅.

Examples of radicals ##STR24## are pyrrolidino, piperidino, morpholino and hexamethyleneimino.

Suitable radicals B² are those mentioned for B¹, provided they conform to the general definition of B².

A compound of the formula I may be prepared by reacting a diazonium compound of an amine of the formula ##STR25## with a coupling component of the formula ##STR26##

Details of the method of preparation may be found in the Examples, where parts and percentages are by weight, unless stated otherwise.

From the point of view of their structure, the dyes of the formula I may be described as disperse dyes, and such dyes can as a rule not be applied to, for example, cotton. However, German Patent No. 1,811,796 describes a process which permits printing such dyes onto cellulose and cellulose-containing textile material. The general principle of the statements made in the said German Patent regarding the process conditions also apply in the case of the dyes according to the present invention. Further, our British Patent Specification No. 1,539,259 and German Published Patent Application No. 2,528,743 describe other processes by means of which the dyes according to the invention can be applied. Amongst these, printing processes are preferred.

The dyes according to the invention give dyeings and prints with excellent fastness characteristics, amongst which, in particular, the wetfastness and in some cases also the lightfastness should be singled out. In the case of prints there is, for example, no staining of any white ground when washing the dyed fabric. Further, the good match of the hues obtained when dyeing polyester/cotton union fabrics deserves mention.

The navy dyes of the formula I are, in addition, exceptionally suitable for the production of black hues or black mixtures.

Dyes of particular importance are those of the formula II ##STR27## where X¹ is chlorine, bromine, methyl, methoxy, cyano, methylsulfonyl, ethylsulfonyl or phenylsulfonyl,

Y is hydrogen, chlorine or bromine,

R³ is C₁ -C₄ -alkoxy,

R⁴ is methyl or C₁ -C₄ -alkoxy and

B¹ has the meaning given above for formula I.

Preferred meanings of B¹ are, independently of one another, hydrogen, C₁ -C₈ -alkyl, allyl and C₂ -C₈ -alkyl(particularly C₂ and C₃ alkyl) which is substituted by C₁ -C₈ -alkoxy, phenoxy, tolyloxy, cyclohexyloxy, benzyloxy, β-phenylethoxy, a carboxylic acid ester group of a total of 2 to 9 carbon atoms, C-acyloxy of a total of 1 to 11 carbon atoms, C₁ -C₈ -alkylaminocarbonyloxy, phenylaminocarbonyloxy, tolylaminocarbonyloxy, chlorophenylaminocarbonyloxy, phenylaminocarbonyloxy, tolylaminocarbonyloxy, chlorophenylaminocarbonyloxy, dichlorophenylaminocarbonyloxy or pyrrolidonyl; cyclohexyl, norbornyl, phenyl-C₁ -C₄ -alkyl, tolyl-C₁ -C₄ -alkyl, β-phenyl-β-hydroxyethyl, phenyl which is unsubstituted or substituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, ethyl, methoxy, ethoxy or pyrrolidonyl, or (CH₂)₃ (OC₂ H₄)_(n) OB, where n is 1 or 2 and B is C₁ -C₄ -alkyl, cyclohexyl, benzyl, phenylethyl, phenyl or tolyl.

In the Examples which follow, only one isomer is referred to in the case of coupling components in which the substituents in the 2- and 6-positions are different from one another; however, it should be noted that the isomer with the 2- and 6-substituents reversed is as a rule also present in the coupling component and hence the corresponding structure is present in the dye.

EXAMPLE 1

0.05 mole of 4'-nitro-2',6'-dichloro-2,5-dimethoxy-4-amino-azobenzene, in the form of the base, is stirred, as an aqueous paste, into 150 parts by volume of 16.5 percent strength hydrochloric acid, containing 2.5 parts of an adduct of sperm oil alcohol and ethylene oxide in the ratio of 1:25, at 40° C. Simultaneously, 15 parts by volume of a 3.33 N sodium nitrite solution are added dropwise, during which addition the reaction temperature rises to 45° C. and the diazonium chloride begins to dissolve. After stirring at ˜45° C. for 30 minutes, during which a further 5 parts by volume of a 3.33 N sodium nitrite solution are added dropwise, the warm diazonium salt solution is run into a solution of 14.5 parts of 2,6-bis-methoxyethylamino-3-cyano-4-methylpyridine in 350 parts by volume of water and 6 parts by volume of 33 percent strength hydrochloric acid at 20° C. Coupling is complete after only 45 minutes, without further addition of a buffer. The coupling mixture is then brought to pH˜11 with 55 parts by volume of 50 percent strength sodium hydroxide solution and the product is filtered off at 60°-65° C. After washing it with hot water, and drying it, a dark blue to black powder of the formula ##STR28## is obtained, which gives a bluish violet solution in N-methylpyrrolidone and dyes or prints polyester and cotton fabrics and polyester/cotton union fabrics in fast navy to black hues.

EXAMPLE 2

0.05 mole of 4'-nitro-2',6'-dichloro-2,5-dimethoxy-4-aminoazobenzene, in the form of the base, is stirred as an aqueous paste into 100 parts by volume of 65 percent strength acetic acid. At the same time, 12 parts of 96 percent strength sulfuric acid and 17.5 parts by volume of 3.33 N aqueous sodium nitrite solution are run in at 15°-20° C. After stirring for from one to two hours at this temperature, the diazonium salt is present in solution and the diazotization is complete, as may be checked by means of a thin layer chromatogram.

The diazonium salt solution thus obtained is now run into a solution, precooled to ˜5° C., of 0.052 mole of 2-(3'-methoxy-propylamino)-3-cyano-4-methyl-6-(3'-phenoxyethoxy-propylamino)-pyridine in 200 parts by volume of 90 percent strength acetic acid. Coupling is effected by dropwise addition of 50 parts by volume of saturated sodium acetate solution.

The reaction mixture is then heated to 80° C. and the product is filtered off and washed with warm acetic acid and finally with hot water. After drying, a bluish black powder of the formula ##STR29## is obtained, which dyes or prints cotton fabrics, polyester fabrics and cotton/polyester union fabrics in fast navy and black hues.

EXAMPLE 3

0.05 mole of 4'-nitro-2',5'-dichloro-2,5-diethoxy-4-amino-azobenzene is stirred, at from 0° to +5° C., into a mixture of 100 parts of 90 percent strength sulfuric acid, 75 parts by volume of 100 percent strength acetic acid and 16 parts of 42 percent strength nitrosylsulfuric acid. On allowing the reaction mixture to come to room temperature, the batch undergoes complete diazotization and the product dissolves.

The resulting diazonium salt solution is run, at ˜5° C., into a solution of 0.052 mole of 2,6-bis-(3'-methoxy-propylamino)-3-cyano-4-methyl-pyridine in 500 parts by volume of 90 percent strength acetic acid, to which 100 parts of sodium acetate have been added beforehand. Further addition of 200 parts of sodium acetate, followed by stirring for several hours whilst the mixture comes to room temperature, results in complete coupling. The mixture is then heated to ˜80° C. and the dye is filtered off at this temperature. After washing it with hot acetic acid and hot water, and drying it, a bluish black powder of the formula ##STR30## is obtained, which dyes or prints cotton fabrics and polyester fabrics in dark blue hues.

The following dyes, having similar tinctorial properties, are obtained in accordance with the methods of Examples 1 to 3.

    __________________________________________________________________________      ##STR31##                                                                     Ex-                                                                            am-                                                                            ple                                                                               R.sup.1  R.sup.2  T.sup.1            T.sup.2             Hue                __________________________________________________________________________     4  OCH.sub.3                                                                               OCH.sub.3                                                                                ##STR32##         NH.sub.2            navy               5  "        "        NH(CH.sub.2).sub.2OCH.sub.3                                                                       "                   "                  6  "        "        NH(CH.sub.2).sub.3OCH.sub.3                                                                       "                   "                  7  "        "        NH(CH.sub.2).sub.2O(CH.sub.2).sub.3CH.sub.3                                                       "                   "                  8  "        "        NHCH.sub.2CH.sub.3 NHCH.sub.2CH.sub.3  "                  9  "        "        NH(CH.sub.2).sub.3CH.sub.3                                                                        NH(CH.sub.2).sub.3CH.sub.3                                                                         "                  10 "        "        NH(CH.sub.2).sub.2OH                                                                              NH(CH.sub.2).sub.2OH                                                                               "                  11 "        "        NH(CH.sub.2).sub.3OH                                                                              NH(CH.sub.2).sub.3OH                                                                               "                  12 "        "        NH(CH.sub.2).sub.2O(CH.sub.2).sub.2OH                                                             NH(CH.sub.2).sub.2O(CH.sub.2).sub.                                             2OH                 "                  13 "        "        NH(CH.sub.2).sub.2OCH(CH.sub.3).sub.2                                                             NH(CH.sub.2).sub.2OCH(CH.sub.3).su                                             b.2                 "                  14 "        "        NH(CH.sub.2).sub.2O(CH.sub.2).sub.3CH.sub.3                                                       NH(CH.sub.2).sub.2O(CH.sub.2).sub.                                             3CH.sub.3           "                  15 "        "                                                                                        ##STR33##                                                                                         ##STR34##          "                  16 "        "                                                                                        ##STR35##                                                                                         ##STR36##          "                  17 "        "                                                                                        ##STR37##                                                                                         ##STR38##          "                  18 "        "                                                                                        ##STR39##                                                                                         ##STR40##          dark blue          19 "        "                                                                                        ##STR41##         NH(CH.sub.2).sub.2OCH.sub.3                                                                        navy               20 "        "        NH(CH.sub.2).sub.3O(CH.sub.2).sub.4OH                                                             "                   "                  21 "        "                                                                                        ##STR42##         "                   "                  22 "        "                                                                                        ##STR43##         "                   "                  23 "        "        N (CH.sub.2).sub.3CH.sub.3 !.sub.2                                                                "                   "                  24 "        "                                                                                        ##STR44##         "                   "                  25 "        "                                                                                        ##STR45##         "                   "                  26 "        "        N (CH.sub.2).sub.2OH!.sub.2                                                                       "                   "                  27 "        "        N (CH.sub.2).sub.2OCH.sub.3 !.sub.2                                                               "                   "                  28 "        "                                                                                        ##STR46##         "                   "                  29 "        "                                                                                        ##STR47##         "                   "                  30 "        "                                                                                        ##STR48##         "                   "                  31 "        "                                                                                        ##STR49##         "                   "                  32 "        "        NH(CH.sub.2).sub.2OH                                                                               ##STR50##          "                  33 "        "        NH(CH.sub.2).sub.2OCH.sub.3                                                                       "                   "                  34 OCH.sub.2CH.sub.3                                                                       OCH.sub.2CH.sub.3                                                                       NHCH.sub.2CH.sub.3 NHCH.sub.2CH.sub.3  "                  35 "        "        NH(CH.sub.2).sub.2OCH.sub.3                                                                       NH(CH.sub.2).sub.2OCH.sub.3                                                                        "                  36 "        "        NH(CH.sub.2).sub.3OCH.sub.3                                                                       NH(CH.sub.2).sub.3OCH.sub.3                                                                        blue               37 "        "        "                                                                                                  ##STR51##          navy               38 O(CH.sub.2).sub.3CH.sub.3                                                               O(CH.sub.2).sub.3CH.sub.3                                                               "                  NH(CH.sub.2).sub.2OCH.sub.3                                                                        "                  39 "        "        NH(CH.sub.2).sub.3OCH.sub.3                                                                       NH(CH.sub.2).sub.3OCH.sub.3                                                                        "                  40 "        "                                                                                        ##STR52##         NH(CH.sub.2).sub.2OCH.sub.3                                                                        "                  41 "        "        NH(CH.sub.2).sub.2OCH.sub.3                                                                        ##STR53##          "                  42 H        OCH.sub.3                                                                               NH(CH.sub.2).sub.3OCH.sub.3                                                                       NH(CH.sub.2).sub.3OCH.sub.3                                                                        deep                                                                           red                43 "        "        NH(CH.sub.2).sub.3CH.sub.3                                                                        NH(CH.sub.2).sub.3CH.sub.3                                                                         deep                                                                           red                44 "        "        NH(CH.sub.2).sub.3OCH.sub.3                                                                       NH(CH.sub.2).sub.3O(CH.sub.2).sub.                                             2OC.sub.6 H.sub.5   deep                                                                           red                __________________________________________________________________________

    __________________________________________________________________________      ##STR54##                                                                     Example                                                                             R.sup.1 R.sup.2 Z    T.sup.1     T.sup.2             Hue                  __________________________________________________________________________     45   OCH.sub.3                                                                              OCH.sub.3                                                                              CN   NH(CH.sub.2).sub.2OCH.sub.3                                                                NH(CH.sub.2).sub.2OCH.sub.3                                                                        navy                 46   "       "       "    NH(CH.sub.2).sub.3OCH.sub.3                                                                NH(CH.sub.2).sub.3OCH.sub.3                                                                        "                    47   "       "       "    "                                                                                           ##STR55##          "                    48   O(CH.sub.2).sub.3CH.sub.3                                                              O(CH.sub.2).sub.3CH.sub.3                                                              CONH.sub.2                                                                          NH(CH.sub.2).sub.2CH.sub.3                                                                 NH.sub.2            "                    49   OCH.sub.3                                                                              OCH.sub.3                                                                              "    NH(CH.sub.2).sub.2OCH.sub.3                                                                NH(CH.sub.2).sub.2OCH.sub.3                                                                        dark blue            50   OCH.sub.2CH.sub.3                                                                      OCH.sub.2CH.sub.3                                                                      "    NH(CH.sub.2).sub.3OCH.sub.3                                                                NH(CH.sub.2).sub.3OCH.sub.3                                                                        "                    __________________________________________________________________________

                                                                                      ##STR56##                                                                       Example R.sup.1 R.sup.2 R.sup.3 R.sup.4 T.sup.1 T.sup.2 Hue                             51 OCH.sub.3 OCH.sub.3 2Cl 5Cl                                          ##STR57##                                                                       NH.sub.2 dark blue                                                              52 " " " " NH(CH.sub.2).sub.2OCH.sub.3 NH(CH.sub.2).sub.2OCH.sub.3 " 53        " " " " NH(CH.sub.2).sub.3OCH.sub.3 NH(CH.sub.2).sub.3OCH.sub.3 greenish        blue                                                                             54 " " " " "                                                                   ##STR58##                                                                        dark blue                                                                       55 " " " "                                                                     ##STR59##                                                                        NH(CH.sub.2).sub.3 OCH.sub.3 "  56 OCH.sub.2CH.sub.3 OCH.sub.2CH.sub.3         " " NH(CH.sub.2).sub.3OCH.sub.3                                                  ##STR60##                                                                       "                                                                               57 O(CH.sub.2).sub.3CH.sub.3 O(CH.sub.2).sub.3CH.sub.3 " " NH(CH.sub.2).       sub.3OCH.sub.3 NH(CH.sub.2).sub.3OCH.sub.3 greenish blue  58 " " " "             ##STR61##                                                                       NH.sub.2 dark blue                                                              59 OCH.sub.3 OCH.sub.3 " 6 Br NH(CH.sub.2).sub.2OCH.sub.3 NH(CH.sub.2).s       ub.2OCH.sub.3 navy 60 " " " " NH(CH.sub.2).sub.3OCH.sub.3 NH(CH.sub.2).su       b.3OCH.sub.3 dark blue  61 OCH.sub.2CH.sub.3 OCH.sub.2CH.sub.3 " "               ##STR62##                                                                       NH.sub.2 navy                                                           O       62 " " " " NH(CH.sub.2).sub.2OCH.sub.3 NH(CH.sub.2).sub.2CH.sub.3 " 63         " " " " NH(CH.sub.2).sub.3OCH.sub.3 NH(CH.sub.2).sub.3OCH.sub.3 dark            blue                                                                             64 " " " " NH(CH.sub.2).sub.3OCH.sub.3                                         ##STR63##                                                                        navy                                                                            65 CH.sub.3 CH.sub.3 2Br " NH(CH.sub.2).sub.3OCH.sub.3 NH(CH.sub.2).sub.       3OCH.sub.3 deep red 66 OCH.sub.3 OCH.sub.3 " " NHCH.sub.2CH.sub. 3              NHCH.sub.2CH.sub.3 navy 67 " " " " NH(CH.sub.2).sub.2OCH.sub.3 NH(CH.sub.       2).sub.2OCH.sub.3 " 68 " " " " NH(CH.sub.2).sub.3OCH.sub.3 NH(CH.sub.2).s       ub.3OCH.sub.3 dark blue  69 O(CH.sub.2).sub.3 CH.sub.3 O(CH.sub.2).sub.3        CH.sub.3 " "                                                                     ##STR64##                                                                       NH.sub.2 navy                                                           O       70 " " " " NH(CH.sub.2).sub.2OCH.sub.3 NH(CH.sub.2).sub.2CH.sub.3 " 71         " " " " NH(CH.sub.2).sub.3OCH.sub.3 NH(CH.sub.2).sub.3OCH.sub.3 dark            blue 72 " " " " NH(CH.sub.2).sub.3CH.sub.3 NH(CH.sub.2).sub.3CH.sub.3 "         73 OCH.sub.3 OCH.sub.3 2CH.sub.3 5Cl NH(CH.sub.2).sub.3OCH.sub.3                 ##STR65##                                                                       "                                                                               74 " " " "                                                                     ##STR66##                                                                        ##STR67##                                                                       "  75 " " " " NH(CH.sub.2).sub.3OCH.sub.3 NH(CH.sub.2).sub.3OCH.sub.3 "         76 " " 2OCH.sub.3 6Br                                                          ##STR68##                                                                        NH.sub.2 bluish violet                                                          77 " " " " NH(CH.sub.2).sub.2OCH.sub.3 NH(CH.sub.2).sub.2OCH.sub.3 " 78        " " " " NH(CH.sub.2).sub.3OCH.sub.3 NH(CH.sub.2).sub.3OCH.sub.3 dark            blue                                                                             79 " " " " "                                                                   ##STR69##                                                                        "                                                                               80 " " 2Br                                                                     ##STR70##                                                                        ##STR71##                                                                       NH.sub.2 bluish violet                                                          81 " " " " NH(CH.sub.2).sub.2OCH.sub.3 NH(CH.sub.2).sub.2OCH.sub.3 navy        82 " " " " NH(CH.sub.2).sub.3OCH.sub.3 NH(CH.sub.2).sub.3OCH.sub.3 dark         blue                                                                             83 " " " " "                                                                   ##STR72##                                                                        "  84 " " " 6CON(CH.sub.2CH.sub.3).sub.2 NH(CH.sub.2).sub.3OCH.sub.3           NH(CH.sub.2).sub.3OCH.sub.3 "                                                    85 " " " " "                                                                   ##STR73##                                                                        "                                                                               86 " " 2OCH.sub.3 5OCH.sub.3 NH(CH.sub.2).sub.3CH.sub.3 NH(CH.sub.2).sub       .3CH.sub.3 "                                                                      87 " " " " NH(CH.sub.2).sub.3OCH.sub.3                                        ##STR74##                                                                        "                                                                               88 " " 2Br 6NO.sub.2                                                           ##STR75##                                                                        NH.sub.2 "                                                                      89 " " " " NH(CH.sub.2).sub.3OCH.sub.3                                         ##STR76##                                                                        "  90 " " " 6SO.sub.2                                                           CH.sub.2OH.sub.3                                                               ##STR77##                                                                        NH.sub.2 "                                                                      91 " " " " NH(CH.sub.2).sub.3OCH.sub.3 NH(CH.sub.2).sub.3OCH.sub.3 "           92 " " " " "                                                                     ##STR78##                                                                       "                                                                               93 " " " "                                                                     ##STR79##                                                                        " "  94 O(CH.sub.2).sub.3CH.sub.3 O(CH.sub.2).sub.3CH.sub.3 " " "              NH.sub.2 navy 95 " " " " NH(CH.sub.2).sub.3OCH.sub.3 NH(CH.sub.2).sub.3OC       H.sub.3 dark blue                                                                96 " " " " "                                                                   ##STR80##                                                                        "                                                                        

                                                                                      ##STR81##                                                                       Example R.sup.1 R.sup.2 R.sup.3 T.sup.1 T.sup.2 Hue                             97 OCH.sub.3 OCH.sub.3 Cl                                                      ##STR82##                                                                       NH.sub.2 medium blue   98 " " " NH(CH.sub.2).sub.3O(CH.sub.2).sub.4OH           NH(CH.sub.2).sub.2OCH.sub.3 "                                                    99 " " " NH(CH.sub.2).sub.2OH                                                  ##STR83##                                                                        dark blue  100 " " " NH(CH.sub. 2).sub.3OCH.sub.3 " medium blue 101 " "        " NH(CH.sub.2).sub.3CH.sub.3 NH(CH.sub.2).sub.3CH.sub.3 "  102 " " "             ##STR84##                                                                       ##STR85##                                                                       "                                                                               103 " " " NH(CH.sub.2).sub.2O(CH.sub.2).sub.2OH NH(CH.sub.2).sub.2O(CH.s       ub.2).sub.2OH dark blue 104 " " " NH(CH.sub.2).sub.2O(CH.sub.2).sub.3CH.s       ub.3 NH(CH.sub.2).sub.2O(CH.sub.2).sub.3CH.sub.3 "                       C       105 O(CH.sub.2).sub.3H.sub.3 O(CH.sub.2).sub.3CH.sub.3 "                        ##STR86##                                                                       NH.sub.2 "                                                                      106 " " " NH(CH.sub.2).sub.2OCH.sub.3 NH(CH.sub.2).sub.2OCH.sub.3 " 107        " " " NH(CH.sub. 2).sub.3OCH.sub.3 NH(CH.sub.2).sub.3OCH medium blue 108        " " " NH(CH.sub.2).sub.3CH.sub.3 NH(CH.sub.2).sub.3CH.sub.3 "  109 " " "        NH(CH.sub.2).sub.3OCH.sub.3                                                      ##STR87##                                                                       "  110 OCH.sub.3 OCH.sub.3 OCH.sub.3 NH(CH.sub.2).sub.3OCH.sub.3               NH(CH.sub.2).sub.3OCH.sub.3 dark blue                                            111 " " " "                                                                    ##STR88##                                                                        "                                                                               112 " " "                                                                      ##STR89##                                                                        " "                                                                             113 O(CH.sub.2).sub.3CH.sub.3 O(CH.sub.2).sub.3CH.sub.3 " NH(CH.sub.2).s       ub.2OCH.sub.3 NH(CH.sub.2).sub.2OCH.sub.3 " 114 " " " NH(CH.sub.2).sub.3O       CH.sub.3 NH(CH.sub. 2).sub.3OCH.sub.3 "  115 OCH.sub.3 OCH.sub.3 CN              ##STR90##                                                                       NH.sub.2 "                                                                      116 " " " NH(CH.sub.2).sub.3OCH.sub.3 NH(CH.sub.2).sub.3OCH.sub.3              greenish blue                                                                    117 " " " "                                                                    ##STR91##                                                                        "                                                                               118 " " "                                                                      ##STR92##                                                                        " "                                                                             119 O(CH.sub.2).sub.3CH.sub.3 O(CH.sub.2).sub.3CH.sub.3SO.sub.2CH.sub.2C       H.sub.3" NH.sub.2 navy                                                           120 " " " NH(CH.sub.2).sub.3OCH.sub.3                                          ##STR93##                                                                        dark blue                                                                       121 " " "                                                                      ##STR94##                                                                        " "                                                                      

    __________________________________________________________________________      ##STR95##                                                                     Ex-                                                                            am-                                                                            ple                                                                               R.sup.1                                                                            R.sup.2                                                                            R.sup.3                                                                          R.sup.4                                                                            R.sup.5                                                                           R.sup.6                                                                            T.sup.1         T.sup.2         Hue                    __________________________________________________________________________     122                                                                               OCH.sub.3                                                                          OCH.sub.3                                                                          Br                                                                               H   Br NO.sub.2                                                                            ##STR96##      NH.sub.2        medium blue            123                                                                               "   "   " "   "  "   NH(CH.sub.2).sub.3OCH.sub.3                                                                    NH(CH.sub.2).sub.3OCH.sub.3                                                                    "                      124                                                                               "   "   " NO.sub.2                                                                           "  "                                                                                   ##STR97##      NH.sub.2        bluish violet          125                                                                               "   "   " "   "  "   NH(CH.sub.2).sub.3CH.sub.3                                                                     NH(CH.sub.2).sub.3CH.sub.3                                                                     medium blue            126                                                                               "   "   " "   "  "   NH(CH.sub.2).sub.3OCH.sub.3                                                                    NH(CH.sub.2).sub.3OCH.sub.3                                                                    "                      127                                                                               "   "   " "   "  "   "                                                                                               ##STR98##      "                      128                                                                               "   "   " OCH.sub.3                                                                          NO.sub.2                                                                          OCH.sub.3                                                                          "               NH(CH.sub.2).sub.3OCH.sub.3                                                                    "                      129                                                                               "   "   " "   "  "   "                                                                                               ##STR99##      "                      __________________________________________________________________________ 

We claim:
 1. A dye of the formula: ##STR100##
 2. A dye of the formula: ##STR101##
 3. A dye of the formula: ##STR102## 